EP0696301B1 - Liant d'adhesion a motifs glutarimides - Google Patents

Liant d'adhesion a motifs glutarimides Download PDF

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Publication number
EP0696301B1
EP0696301B1 EP94915186A EP94915186A EP0696301B1 EP 0696301 B1 EP0696301 B1 EP 0696301B1 EP 94915186 A EP94915186 A EP 94915186A EP 94915186 A EP94915186 A EP 94915186A EP 0696301 B1 EP0696301 B1 EP 0696301B1
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EP
European Patent Office
Prior art keywords
polymer
polyamide
layer
binder
pvdf
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94915186A
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German (de)
English (en)
French (fr)
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EP0696301A1 (fr
Inventor
Serge Lorek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Filing date
Publication date
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09J127/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to an adhesion binder with glutarimide units and its application as a barrier material. It relates more particularly to coextrusion with a layer or film of fluoropolymer and in particular of polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • EP 3,449 describes the coextrusion of PVDF with polyurethanes (PU); he it is not necessary to use a binder.
  • FR 2,436,676 describes the coextrusion of PVDF with polymethyl methacrylate (PMMA) and a poly (acrylonitrile-butadiene-styrene) (ABS), the PMMA film being between the PVDF and ABS films.
  • PMMA polymethyl methacrylate
  • ABS poly (acrylonitrile-butadiene-styrene)
  • Another example was done with polyvinyl chloride (PVC) instead of ABS.
  • EP 354,071 and DE 2,715,185 describe treatment methods for improve the adhesion of PVDF with polymers not compatible with it.
  • the treatment method of EP 354 071 consists in applying to the surface PVDF intended to be in contact with the incompatible polymer of the powder PVDF and then heat to at least 130 ° C.
  • the treatment method for DE 2 715 185 consists in applying to the PVDF surface intended to be in contact with the incompatible polymer a PU solution in a polar aprotic solvent.
  • the invention relates to the use of a polymer A which contains the following motifs: in which R 1 and R 2, which are identical or different, represent H or a linear or branched alkyl having from 1 to 20 carbon atoms in which (i) R 4 and R 5, which are identical or different, represent H or a linear or branched alkyl having 1 to 20 carbon atoms, (ii) R 3 represents H, an alkyl, cycloalkyl, aryl, alkaryl, aralkyl or a heterocycle in which R 6 represents H or a linear or branched alkyl having from 1 to 20 carbon atoms in which R 7 represents H or a linear or branched alkyl having from 1 to 20 carbons and R 8 represents a linear or branched alkyl having from 1 to 20 carbon atoms, as adhesion binder of fluorinated polymer, preferably polyfluoride vinylidene (PVDF) allowing it to adhere to polymers which are incompatible with it.
  • PVDF
  • the polymer A can for example be a derivative of PMMA. It can be obtained by reacting PMMA with ammonia or amines. Other polymers A and their preparation methods are described in EP 216.505. The reasons represent from 1 to 6% by weight of the copolymer A.
  • fluoropolymer also means mixtures of at least 70% by weight of the above with other polymers.
  • PVDF fluorinated polymers
  • PVDF also means mixtures of the above with at least one other thermoplastic polymer, with provided that at least 50% by weight of VF2 units is present in the mixture.
  • polyamides for example polyamides, copolyamides, alloys polyamides, alone or as a mixture.
  • PA polyamides
  • PA polyamides
  • Polyamide alloys can be those made up of a matrix polyamide in which are dispersed particles of another polymer such as those described in US Patent 4,174,358.
  • Polyamides can contain plasticizers.
  • the invention also relates to mixtures of polymer A with a polymer to lower its modulus of elasticity.
  • the binder consisting of polymer A is sometimes too rigid for certain applications, so it is useful to mix with another polymer to make it less rigid.
  • Fluoropolymer can be used modified by elastomers or a polymer compatible with polymer A.
  • the binder according to the invention can be used as a coextrusion binder.
  • the invention also relates to the three-layer material, namely successively a layer of fluoropolymer, a layer of the binder according to the invention and a layer of a polymer incompatible with the fluoropolymer.
  • These layers can be plates or films; they can be flat or cylindrical. These are for example pipes or tubes.
  • the polymer incompatible with the fluoropolymer is a polyamide, a copolyamide or a polyamide alloy.
  • This three-layer material can be prepared by usual techniques of coextrusion or overmolding.
  • a particularly interesting form of this material is a tube whose outer layer is polyamide and the layer interior in fluoropolymer, and preferably in PVDF. This tube is useful for the supply of petrol to automobile engines.
  • Tubes must be as least permeable to products as possible petroleum and their additives, in particular methanol.
  • polyamide tubes are commonly used in automobile industry.
  • Polyamides represent an ideal material for this tube application, their mechanical resistance being excellent and their flexibility being sufficient for a tube to support, without breaking, during practically the entire life of a vehicle, the accumulation of bending movements.
  • These polyamide tubes no longer meet the new requirements of car manufacturers regarding concerns permeability.
  • the sensitivity of polyamide tubes is manifested by a swelling of the tube resulting in a decrease in mechanical properties and dimensional changes.
  • the object of the invention consists in sheathing the internal wall of the tube polyamide with a layer of fluoropolymer, preferably PVDF.
  • the layer of fluoropolymer is preferably as fine as possible in order to keep the maximum flexibility of polyamide, knowing that fluoropolymers and including PVDF, are not particularly famous for their properties in flexibility.
  • Polyamide-based tubes for food are recommended in petrol engines generally having an external diameter of 6 to 12 mm, the thickness of the internal layer of fluoropolymer, preferably PVDF, is between 10 ⁇ m and 1 mm and that of the polyamide between 0.8 and 1.8 mm, an intermediate layer of adhesion binder between the polyamide and the fluoropolymer from 10 ⁇ m to 1 mm completing the tube.
  • the thickness of the internal layer of fluoropolymer preferably PVDF
  • an intermediate layer of adhesion binder between the polyamide and the fluoropolymer from 10 ⁇ m to 1 mm completing the tube.
  • a tube which does not have a connection between the fluoropolymer and the polyamide cannot have good flexibility and therefore cannot be folded or easily bent by hot forming; in this case the thinnest material folds during the operation.
  • the two layers do not adhere to each other, the condensation possible gases between the two layers, over time, can cause the deformation of the thinnest part of the tube.
  • the thickness of the fluoropolymer layer, inside the tube is very thin, for example from 10 to a few tens of ⁇ m, and without adhesion, a vacuum in the tube irreversibly deforms the fluoropolymer film rendering the tube unusable.
  • a tube consisting of an internal layer of fluoropolymer bonded by the adhesion binder according to the invention to an external layer of polyamide reduces the permeability by a factor of 10 compared to that of a tube equivalent in polyamide, while retaining the other properties, such as resistance to cold shock, within the limits of the specifications of the Car manufacturers.
  • the fuel tube can be formed a central layer of fluoropolymer, preferably PVDF, with each of side, a layer of the binder of the invention and a polyamide layer, that is to say that the tube has 5 layers: PA / binder based on polymer A / fluoropolymer / binder based on polymer A / PA.
  • reground tubes i.e. batches of polyamide-based tubes and in particular multilayer structures according to the invention, ground and optionally mixed with the polyamide.
  • the polymer-based binder A is mixed with fluoropolymer and / or fluoropolymer modified with elastomer or plasticized, and optionally an elastomer compatible with A, such as cited above, to make it less rigid.
  • the binder based on polymer A also contains of the fluoropolymer, it is preferred that the fluoropolymer present in the binder is the same as that found in the adjacent fluoropolymer layer.
  • MBS designates impact modifiers which are in the form of particles with a styrene / butadiene rubber core and a shell acrylic / styrene.
  • the petrol tubes thus produced have a resistance exceptional in alcohol, alcoholic essences and heat.
  • the polymers incompatible with the fluorinated polymers are polyamides.
  • PVDF / Liant / PA composites are tubes, but could be films, cans or tanks.
  • the standard used to judge the resilience of tubes is the DIN standard. 53453. The tests are carried out at -40 ° C.
  • the peeling tests on tubes are carried out on a dynamometer at a speed of 200 mm / min and for a peeling angle of 180 °.
  • Adhesion is measured in g / cm.
  • the following correspondence is used: Interfacial adhesion> 10,000 g / cm (non-laminating structure) ++++ 6000 g / cm ⁇ Interfacial Adhesion ⁇ 10000 g / cm +++ 2000 g / cm ⁇ Interfacial Adhesion ⁇ 6000 g / cm ++ Interfacial adhesion ⁇ 2000 g / cm 0
  • Polyamide # 1 is a PA-12 plasticized with 7.5% by mass of n-Butyl Benzene Sulfonamide (BBSA), having a flexural modulus of 450 MPa (ISO Standard 178) and a Charpy impact resilience with a notch of 9 kJ / m 2 at -40 ° C (ISO Standard 179).
  • BBSA n-Butyl Benzene Sulfonamide
  • Polyamide # 2 is a PA-11 plasticized with 13% by mass of BBSA, with a flexural modulus of 350 MPa (ISO Standard 178).
  • PVDF # 1 10C / 10 PVDF # 1 is a homopolymer of Fluidity 13 g / 10 min at 230 ° C under 5 kg (Standard ISO1133). This example illustrates the low resilience of PVDF compared to PA. Multilayer pipes with internal layer of PVDF.
  • PVDF # 2 is a homopolymer of Fluidity 8 g / 10 min at 230 ° C under 5 kg (ISO1133 standard).
  • PVDF # 3 is a PVDF # 1 modified with 2.5% of Carbon Black in order to make it conductive.
  • Liant # 1 is a mixture obtained by extrusion on a twin screw extruder PVDF # 1 (50% by mass), an acrylic-imide copolymer comprising acidic groups in its structure and having a flexural modulus of 4100 MPa (ISO Standard 178) (15%) and an impact modifier such as Core-Shell Methyl Methacrylate Butadiene Styrene (MBS) (35%).
  • PVDF # 1 an acrylic-imide copolymer comprising acidic groups in its structure and having a flexural modulus of 4100 MPa (ISO Standard 178) (15%) and an impact modifier such as Core-Shell Methyl Methacrylate Butadiene Styrene (MBS) (35%).
  • Liant # 2 is a mixture obtained by extrusion on a twin screw extruder a PVDF of Fluidity 2 g / 10 min at 230 ° C under 5 kg (Standard ISO1133) (90%) and same copolymer of acrylic-imide type (10%).
  • Liant # 3 is similar to Liant # 2 but contains more copolymer of acrylic-imide type (20%).
  • the fluorinated copolymer is a copolymer of VF2 (90 mol%) and VF3 (10%) obtained by a suspension process.
  • the films used for the test are obtained by extrusion through an appropriate die.
  • the three-layer film is obtained by pressing of the films on a laboratory plate press at 230 ° C for 60 s.
  • Example 11 shows that the coextruded tubes have perfect adhesion between the layers.
  • the tube tested is a Polyamide # 2 / Binder # 1 / PVDF # 1 structure. Pipe sections are immersed for 1000h at 60 ° C in the selected aggressive fluid. The peel test is carried out immediately after immersion. The peeling is initiated at the weakest interface. These Examples show the persistence of a very good adhesion under very severe conditions. Retention of Membership after Exposure to Aggressive Fluids.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
EP94915186A 1993-04-30 1994-04-28 Liant d'adhesion a motifs glutarimides Expired - Lifetime EP0696301B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9305156A FR2705683B1 (fr) 1993-04-30 1993-04-30 Liant d'adhésion à motifs glutarimide et son application comme matériau barrière.
FR9305156 1993-04-30
PCT/FR1994/000488 WO1994025524A1 (fr) 1993-04-30 1994-04-28 Liant d'adhesion a motifs glutarimides

Publications (2)

Publication Number Publication Date
EP0696301A1 EP0696301A1 (fr) 1996-02-14
EP0696301B1 true EP0696301B1 (fr) 1998-12-02

Family

ID=9446626

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94915186A Expired - Lifetime EP0696301B1 (fr) 1993-04-30 1994-04-28 Liant d'adhesion a motifs glutarimides

Country Status (13)

Country Link
US (2) US5795939A (no)
EP (1) EP0696301B1 (no)
JP (1) JP3554323B2 (no)
KR (1) KR100308566B1 (no)
AT (1) ATE174046T1 (no)
AU (1) AU697122B2 (no)
CA (1) CA2161653A1 (no)
DE (1) DE69415003T2 (no)
ES (1) ES2126756T3 (no)
FI (1) FI955131A0 (no)
FR (1) FR2705683B1 (no)
NO (1) NO308365B1 (no)
WO (1) WO1994025524A1 (no)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9913933B2 (en) 2013-03-15 2018-03-13 St. Jude Medical, Cardiology Division, Inc. Multilayered catheter shaft containing polyvinylidene fluoride polymers
US10238776B2 (en) 2010-12-29 2019-03-26 St. Jude Medical, Atrial Fibrillation Division, Inc. Hydrophobic catheter and composition

Families Citing this family (31)

* Cited by examiner, † Cited by third party
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DE4410148A1 (de) * 1994-03-24 1995-09-28 Huels Chemische Werke Ag Mehrschichtiges Kunststoffrohr
CN1082440C (zh) * 1994-08-19 2002-04-10 美国3M公司 含有含氟聚合物层的多层组合物
US5658670A (en) * 1994-08-19 1997-08-19 Minnesota Mining And Manufactury Company Multi-layer compositions having a fluoropolymer layer
DE19507026A1 (de) * 1995-03-01 1996-09-05 Huels Chemische Werke Ag Thermoplastische Mehrschichtverbunde
FR2742445B1 (fr) * 1995-12-19 1998-01-16 Atochem Elf Sa Compositions antistatiques et adherentes a base de polyamide
US5891373A (en) * 1996-05-23 1999-04-06 Eagle-Picher Industries, Inc. Process of making a multi-layer tube
AU3438797A (en) * 1996-06-26 1998-01-14 Elf Atochem S.A. Metal-adhesive polyvinylidene fluoride compositions
WO1998005493A1 (en) * 1996-08-05 1998-02-12 E.I. Du Pont De Nemours And Company Coextruded laminate
US5855977A (en) * 1996-08-26 1999-01-05 Minnesota Mining And Manufacturing Company Multi-layer compositions comprising a fluoropolymer
US6077609A (en) * 1997-06-27 2000-06-20 Dyneon Llc Composite articles including fluoropolymers and non-fluorinated polymers and method for making the same
US6767948B1 (en) * 1999-12-22 2004-07-27 3M Innovative Properties Company Polyolefin polymer and catalyst blend for bonding fluoropolymers
WO2001060606A1 (fr) * 2000-02-18 2001-08-23 Daikin Industries, Ltd. Moulage de resine en couches et article moule multicouche
EP1211288A1 (fr) * 2000-12-01 2002-06-05 Atofina Composition conductrice à base de polymère fluoré
ATE327463T1 (de) 2001-03-23 2006-06-15 Arkema Mehrschichtiges rohr aus polyamiden und fluoropolymeren für den kraftstofftransport
DE602004011101T2 (de) * 2003-12-01 2009-01-02 Arkema France, S.A. Verwendung eines Rohres aus gepfropftem Fluorpolymer, hergestellt durch Bestrahlung, für den Kraftstofftransport
US20050118372A1 (en) * 2003-12-02 2005-06-02 Anthony Bonnet Use of a structure based on a grafted fluoropolymer for storing and transporting chemicals
ATE393702T1 (de) * 2003-12-02 2008-05-15 Arkema France Verwendung einer struktur auf basis eines gepfropften fluorpolymeren für die aufbewahrung und den transport von chemischen produkten.
FR2876769B1 (fr) 2004-10-19 2007-01-05 Arkema Sa Tube multicouche a base de polyamide et de polymere fluore pour le transfert de fluides
FR2876771B1 (fr) 2004-10-19 2007-01-05 Arkema Sa Tube multicouche a base de polyamide et de polymere fluore pour le transfert de fluides
FR2876766B1 (fr) 2004-10-19 2007-01-05 Arkema Sa Tuyau a base d'elastomere vulcanise et de polymere fluore modifie
FR2876767B1 (fr) 2004-10-19 2007-02-02 Arkema Sa Tube multicouche a base de polyamide et de polymere fluore pour le transfert de fluides
AU2006253984B2 (en) * 2005-06-02 2010-12-16 Arkema France Multilayer tube for transporting water or gas
FR2886707B1 (fr) * 2005-06-02 2007-08-17 Arkema Sa Utilisation d'un tube a base de polymere fluore greffe par irradiation pour le transport de fluides sous pression
FR2886708B1 (fr) * 2005-06-02 2007-08-17 Arkema Sa Utilisation de polymere fluore modifie pour le transport d'eau ou de gaz
EP1888957A2 (en) * 2005-06-09 2008-02-20 Uponor Innovation Ab An improved multilayer pipe
EP2077941A4 (en) * 2006-11-01 2009-10-28 Arkema Inc BASED ON A POLYAMIDE AND AN ETHYL-VINYL-ALCOHOL OR POLYVINYL-ALCOHOL, MULTILAYER FLUID TRANSFER TUBE
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US9913933B2 (en) 2013-03-15 2018-03-13 St. Jude Medical, Cardiology Division, Inc. Multilayered catheter shaft containing polyvinylidene fluoride polymers

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ES2126756T3 (es) 1999-04-01
JP3554323B2 (ja) 2004-08-18
FI955131A (fi) 1995-10-27
FI955131A0 (fi) 1995-10-27
EP0696301A1 (fr) 1996-02-14
NO308365B1 (no) 2000-09-04
AU6660294A (en) 1994-11-21
KR100308566B1 (ko) 2001-11-30
NO954233D0 (no) 1995-10-23
KR960701946A (ko) 1996-03-28
FR2705683A1 (fr) 1994-12-02
FR2705683B1 (fr) 1995-08-04
ATE174046T1 (de) 1998-12-15
DE69415003T2 (de) 1999-07-01
US5939492A (en) 1999-08-17
WO1994025524A1 (fr) 1994-11-10
AU697122B2 (en) 1998-09-24
JPH08509519A (ja) 1996-10-08
US5795939A (en) 1998-08-18
DE69415003D1 (de) 1999-01-14
NO954233L (no) 1995-10-23
CA2161653A1 (fr) 1994-11-10

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